P-POLYPHENYL FROM BENZENE-LEWIS ACID CATALYST-OXIDANT . REACTION SCOPE + INVESTIGATION OF BENZENE-ALUMINUM CHLORIDE-CUPRIC CHLORIDE SYSTEM
P-POLYPHENYL FROM BENZENE-LEWIS ACID CATALYST-OXIDANT . REACTION SCOPE + INVESTIGATION OF BENZENE-ALUMINUM CHLORIDE-CUPRIC CHLORIDE SYSTEM
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DOI：
10.1021/jo01024a023
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发表时间：
1964-01-01
影响因子：
3.6
通讯作者：
OZIOMEK, J
中科院分区：
文献类型：
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作者：
KOVACIC, P;OZIOMEK, J
在氯化铝-氯化铜催化苯聚合反应中，对聚苯的产率随加水量的增加而增加。聚合物产率达到最大值，几乎定量，在AlClg-CuCl摩尔比为2：1。氧化剂还原生成的氯化亚铜以C6 H6· AlClg-CuCl络合物的形式存在。加入大量氯化亚铜完全抑制反应，而少量氯化亚铜则起促进作用。以卤化铜为氧化剂，氯化铝、溴化铝和五氧化二锑表现出催化活性。在卤化铝催化剂的存在下，聚合发生与氧化剂，氯化铜，溴化铜，二氧化铅，二氧化锰，二氧化氮，三氧化二氮，四氯对苯醌，和对苯醌。有证据表明，氮氧化物和四氯对苯醌会导致链终止。最近的研究表明，在芳香族单体-路易斯酸催化剂-氧化剂体系中，芳香核可以顺利聚合。这构成了第一种情况，其中芳香族单体在明确定义的聚合中起作用，导致均聚物。例如，在温和的条件下，用氯化铝-氯化铜处理，苯被转化为对聚苯。
In the polymerization of benzene by aluminum chloride-cupric chloride, the yield of p-polyphenyl varied in-versely with the amount of added water. Polymer yield attained a maximum value, almost quantitative, at an AlClg-CuCL molar ratio of 2: 1. The cuprous chloride formed by reduction of the oxidant is present as a C6H6· AlClg-CuCl complex. Large amounts of added cuprous chloride inhibited the reaction completely, whereas smaller quantities acted as a promoter. With cupric halide as oxidant, aluminum chloride, aluminum bromide, and antimony pentachloride exhibited catalytic activity. In thepresence of aluminum halide catalyst, polymerization occurred with the oxidizing agents, cupric chloride, cupric bromide, lead dioxide, manganese dioxide, nitrogen dioxide, nitrogen trioxide, chloranil, and p-benzoquinone. There was evidence of chain termination by the nitrogen oxides and chloranil. The theoretical aspects are treated.Recently, it was shown2 that the aromatic nucleus can be polymerized smoothly in the system, aromatic monomer-Lewis acid catalyst-oxidant. This con-stituted the first case wherein an aromatic monomer functioned in a well defined polymerization leading to homopolymer. For example, benzene was converted to p-polyphenyl on treatment with aluminum chloride-cupric chloride under mild conditions.